A method performs a planar and cross-sectional etching of semiconductor devices made up of multiple layers of dissimilar materials, like metals and dielectrics. The method results in the removal of multiple layers with the aim of either exposing a single layer of interest or cross-sectioning several layers to perform various applications including but not limited to, nanoprobing, circuit edit and failure analysis. The method comprises directing an ion beam toward a defined area on the semiconductor device in the presence of an etching agent, thereby removing at least a portion of the mixed metal and dielectric layer and producing a recess with at least one substantially smooth and planar surface in the milled area. The used etching agent comprises oxidizing and reducing elements in a ratio optimized such that the quantity of oxidizing elements is one element more than the quantity of reducing elements.
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1. A method of etching one or more of mixed metal and dielectric layer, from an area on a semiconductor device, the method comprising:
defining the area on the semiconductor device to be etched, the area including at least several layers comprised of mixed metal and dielectric combined in the semiconductor device;
directing a first etching agent toward the defined area on the semiconductor device, wherein the first etching agent comprises a core structure, —C—O—O—, —C(=O)—O—, —C—O—N—, —C(=O)—N—, —C—N—N— or —C(N)—N— and further comprises an oxidizing element selected from a group of fluorine, chlorine, oxygen, nitrogen and reducing elements which are carbon in ratio, wherein a quantity of the oxidizing elements is one element more than a quantity of the reducing elements and the quantity of reducing elements is at most three; and
directing an ion beam toward the defined area on the semiconductor device in a presence of the first etching agent, thereby removing at least a portion of the mixed metal and dielectric layers and producing a recess with at least one substantially smooth and planar surface in a milled area on an object.
12. A method of etching one or more of mixed metal and dielectric layer, from an area on a semiconductor device, the method comprising:
defining the area on the semiconductor device to be etched, the area including at least several layers comprised of mixed metal and dielectric combined in the semiconductor device;
directing a first etching agent toward the defined area on the semiconductor device, wherein the first etching agent comprises a core structure —COO—, —CON—, or —CNN— and further comprises an oxidizing element selected from a group of fluorine, chlorine, oxygen, nitrogen and reducing elements which are carbon in ration, wherein a quantity of the oxidizing elements is one element more than a quantity of the reducing elements and the quantity of reducing elements is at most three; and
directing an ion beam toward the defined area on the semiconductor device in a presence of the first etching agent, thereby removing at least a portion of the mixed metal and dielectric layers and producing a recess with at least one substantially smooth and planar surface in a milled area on an object,
wherein etching the defined area of the semiconductor device with the first etching agent comprises:
a first etching step wherein at least a portion of the mixed metal and dielectric layers is etched with a first beam of energy, and
a second etching step wherein the portion of the mixed metal and dielectric layers etched in the first etching step is fine etched using a second beam of energy, wherein the first beam of energy is higher than the second beam of energy.
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This application, filed under 35 USC 371, is a United States National Stage Application of International Application No. PCT/CZ2017/000021 filed Apr. 4, 2017, the disclosure of which is incorporated herein by reference.
The present invention relates to a method for gas-assisted etching of dissimilar materials by ion beam irradiation and is applicable, for example to uniform removing of metal and dielectric material for creating smooth and planar surface on semiconductor device.
Etching is a well-known technique in semiconductor industry which is used for removal of material from semiconductor devices. The purpose of the removal is to extend accessibility of interesting areas. The etching process may have two modes. The first mode is a so called planar etching or deprocessing contains a layer-by-layer removal of thin layers to the die of the semiconductor device. The second mode is called cross-section etching and produces a recess in the semiconductor device in which the cross-section of more layers may be observed. The etching is a frequently employed technique in semiconductor industry and also by material analysis groups in research institutes and universities. Commercially etching may be performed by reactive ion etching, wet chemical etching or mechanical etching comprise polishing or cutting. Out of these, mechanical etching is the most common technic used for large area removal of metal and dielectrics mixed or not. Mechanical etching approach is very abrasive, with a likely formation of slurry sitting between layers of the device and so requiring additive cleaning procedures. The surfaces obtained with mechanical etching are generally non-planar surfaces with an apparent gradient at the surface and a poor reliability in term of small structures localization. With the nature of the semiconductor devices growing more sensitive to these side-effects are likely to fail through precise defect localization, nanoprobing, C-AFM measurements, circuit edit or any other electrical tests.
Mechanical etching may be replaced with much more precise advanced instruments like a focused ion beam device or broad ion beam device which may perform etching in a localized fashion. Nearby area is almost unaffected or the effect is only in the range of few micrometers. The ion beam device creates a stream of ions targeting with great accuracy a pre-chosen area to sputter atoms from the sample. Ion Beam (IB) when scanning over a given area modifies a sample in different ways, depending on the energy of the incoming ions. Ion beam devices employ a variety of ions from He to Xe, usually differentiated by their mass and consequently their interaction with the target surface.
The process of material removal is controlled as it can be easily monitored online by collecting signal from the sputtered ions using different detectors in a FIB-SEM system. Further widening the application base of FIB-SEM systems, gas assisted etching (GAE) techniques are now widely employed.
The “maze” like geometry of the conductive metal lines running through the dielectric material in semiconductor device stacked in 3-dimensions makes planar etching and cross-section etching more challenging when only the FIB is used. FIB interactions with a sample surface are different depending on the composition and/or the crystallinity of the targeted surface. This leads to pre-determination in sputtering rates for every material using the same set of FIB conditions. These interactions can be modified when reacting molecules are introduced as etching agent in the form of gas or vapor using a gas injection system (GIS) in the working area. The basic principle of this method is the introduction of a gas containing suitable chemical form of the desired material into the sample chamber. When injecting this favorable chemical gas agent into the chamber during the etching of two or more dissimilar materials can enable sputtering at equal rates leading to a smooth planar surface.
Two main reactions may generally be observed when introducing the gas near the sample surface: surface modification via etching and material deposition. Gas assisted etching can be used for either modifying the etching behavior of certain materials because of the presence of gases or the gas agents under the ion beam enables deposition of precursor material onto the target surface. With a reactive gas as an etching agent under the influence of beam can help increase or decrease the etching rates of some materials due to the localized chemical reactions. On one hand, when volatile species are formed, the sputtering rate Is increased and less material redeposition is observed. On the other hand, harder layers can also be created by the deposition of the gas molecules on to the surface and simultaneous diminution of the sputtering rate is observed. Such diversified applications of the sputtering rate are exploited to perform selective etching or planar etching on semiconductor devices. With a reactive etching agent, the ion beam etching due to the ion beam can be enhanced or reduced due to local chemical reactions.
The U.S. Pat. No. 6,900,137 uses XeF2 to etch both organic dielectric and metal layer in a controlled manner by increasing the dwell times of the FIB.
U.S. Pat. No. 7,008,803 is using GAE with variable position endpoint detector to determine the dwell time of single point etching until the end of etched layer.
In patent application 2013/0118896 FIB is used for homogenous removal of dissimilar materials using a rotating sample stage and an adjustment of the FIB operating conditions during the process. This method needs a precise control of the etching rate of each material present at the sample surface and the number of parameters that needs to be controlled during the milling. It requires producing hierarchical circuit schematics for each sample using the acquired surface data from each removed layer.
In U.S. Pat. No. 9,064,811 is reported a group of etching agents for GAE causing the equal etching rate of dissimilar material by slowing down etching rate of dielectric compared to metallic compounds which are selected from the group containing acetate/nitroacetate and short hydrocarbons chain. Patent specifically enlists methyl acetate, ethyl acetate, ethyl nitroacetate, propyl acetate, propyl nitroacetate, nitro ethyl acetate, methyl methoxyacetate or methoxy acetylchloride as the agents for GAE.
Semiconductor industry is growing at a very fast pace with newer challenges with each passing day. Materials employed, more and more complex architectures with constant need to further miniaturization to increase the number of transistors in smaller areas and so the diminution of their size turned exponentially the condensed density of the circuits. Although, in the references cited above, different methods for producing planar surface using ion beam device are discussed, there is a wide variety of etching agents which can be used for planar etching even more regarding the increasing number of material constituting the next generation of semiconductor devices as well as the architecture used for the circuits. Many methods can suited for etching a given set of metal-dielectric combination and be more effective than using a FIB alone on other combinations, while keeping the unwanted side effects like redeposition from the gas by-products to bare minimum.
Some of them may be etched using existing GAE methods. It is more effective to have a variety of etching agents in selection to choose the one with the best performance for the method of etching dissimilar materials with approximately the same etching rates.
The method described hereunder uses selected etching agents for semiconductor material removal from thick copper layers directly exposed after de-capping to a very thin dense copper layers which are just above the transistor contact layer (TCL). It is often required that during etching, dissimilar materials should have the same etching rates. The selected etching agent must include enough oxidizing elements to adjust etching rate of metal and enough reducing elements to adjust the etching rate of dielectric to the level where both dissimilar materials are etched at approximately the same etching rate.
The presence of a high energy ion beam (IB) such as focused ion beam or broad beam with a beam energy of at least, 5 keV, together with the etching agent and semiconductor device produces reactive elements by breaking the inter-elemental bond of compounds in the working chamber especially in the active ion beam area. The active ion beam area is the area along the trajectory of the ion beam and in the space where the ion beam reaches the surface of the semiconductor device. These reactive elements associated with the large amount of electrons produced by the interaction of the ion beam with either the sample surface or with etching agent may react with the constitutive elements and form other molecules. To create a volatile compound favoring etching, the GIS must deliver an etching agent or combination of etching agents containing elements necessary to produce a targeted volatile compound. For better control of the simultaneous milling of dissimilar materials containing metal and dielectric, a suitable combination of the surface composition and the elements introduced by the GIS must be found in order to allow the desired surface reactions. The elements required to create volatile molecules may contain carbon (C), oxygen (O), halogenated elements like flourine (F) and chlorine (Cl) and nitrogen (N). Simultaneous etching of the metallic constitutive-elements of the semiconductor device must be considered along with etching of the dielectric which must also be controlled to obtain specified delayered-surface roughness. This dielectric may have varied compositions consisting of more elements since the most common dielectrics are the SiOx and SixNy types. Up to now; carbon is added in as a named low-k dielectric such as potential substrates based on GaAs or GaN materials. The metal used in semiconductor device may be copper, cobalt, aluminum, tungsten, and tantalum. When sputtered from the sample and ejected by the ion beam interaction with the dielectric, the amount of reactive molecules from dielectric milling increases. Without the presence of complementary molecules brought in by a GIS, similar to metal etching (as described above), it is difficult to control their milling rate. Thus, to reach a controlled etching rate with an approximately 1:1 ratio between all the constitutive elements of a selected sample, the etching rate of all materials with and without the addition of chemistry must be taken into account. The etching agent used for GAE may include oxidizing elements with one or several different chemical functionalities using nitrogen, oxygen and halogen (F, CI) and a reduction element preferably in the form of carbon. Nitrogen is required to produce volatile metal-nitrogen molecules such as copper nitride. Halogens are required to produce metal-halides or silicon halides. Oxygen may be used to produce volatile COx molecules with C-contained in low-k dielectric. This volatile molecule formation will aid their pumping out of the chamber, thus decreasing the redeposition of by-products generated during GAE using ion beam.
The ratio of all these injected elements must be controlled, considering the sample composition, to reach a level of surface uniformity and roughness of the final layer. The chemical compounds in agreement with the invention from which the etching agent is selected comprise —COO—, —CON—, or —CNN— core structure in combination with other elements according to the requirement for oxidation/reduction ratio (oft), The etching according the invention may be a planar etching where the substantially planar surface made by ion beam is parallel to the metal or dielectric layers in the semiconductor device or a cross-section etching where the substantially planar surface is offset to the metal or dielectric layers in range of 10-170°.
Based on this approach for etching of dissimilar materials such as metal and dielectrics, the amount of oxidizing (o) and reducing (r) elements present in the etching agent should be balanced. The best ratio for etching of dissimilar materials was determined as: [o=r+1], preferably 3 oxidizing and 2 reducing elements for the most common combinations of dielectric and metal such as silicon dioxide and copper. With an increasing number of reducing elements in the etching agent it is more difficult to predict the amount of reactive fragments and to ensure their gaseous character in working chamber. The number of reducing elements in the etching agent ensuring the appropriate function is up to 3 but also the etching agents with a higher number of reducing elements may have required properties. Reducing elements in the etching agent must be C and oxidizing elements must be selected from the group of F, Cl, O and N. In a preferred embodiment, the etching agent may comprise one chemical compound from a group: Ammonium ethanoate, Chloroacetamide, Fluoroacetamide, Methyl Carbamate, N-Nitrosodiethylamine.
In further embodiment according to the invention, the etching of a semiconductor device may release a large number of secondary oxidizing and reducing elements from the semiconductor device into the working chamber. These secondary oxidizing and reducing elements may significantly contribute to the etching process and would as such affect the total amount of oxidizing and reducing elements that would need to be introduced via the GIS during etching. If the number of secondary elements is high enough for causing element disproportion influencing the etching process and/or tends toward non-uniform etching of dissimilar materials, the composition of the etching agent or mixture of etching agents needs to be adjusted. Good adjustment of dissimilar material etching performance was observed for etching agents or mixture of etching agents with the number of elements in etching agent within a range from [o−r=−1] to [o−r=3]. If the etching of copper is faster than the dielectric, more reducing elements need to be included. Likewise, if the etching of dielectric is faster than copper more oxidizing elements are required. The non-uniform etching ratio may be adjusted by the etching agent containing one compound from: Acetic Acid, Ethyl Formate, Ammonium Bicarbonate, Hydrazine Acetate, Diethyl imidodicarbonate, Ammonium Oxalate and water. The etching process may be monitored online or in intervals with SEM or FIB device equipped with appropriate signal detection device and method.
In preferred embodiments, the mixture of etching agents comprises at least first etching agent from: Ammonium ethanoate, Chloroacetamide, Fluoroacetamide, Methyl Carbamate, N-Nitrosodiethylamine and at least one second etching agent from: Acetic Acid, Ethyl Formate, Ammonium Bicarbonate, Hydrazine Acetate, Diethyl imidodicarbonate and water.
In a further embodiment in line with the invention, the etching agent contains an R—CO—R core structure. The R in the formula may comprise any of the elements which together with the core structure fulfill the conditions of the ratio of oxidizing and reducing elements. The R—CO—R structure contains a strong C—O double covalent bond and other inter-elemental bonds e.g. C—H, C—C, C—NH2 which have lower bonding energy than the C—O double covalent bond. The molecules may be fragmented in the gas phase by high energy collision induced dissociation (CID). In typical CID, the molecular ions are usually accelerated to high kinetic energies by an electrical potential and then allowed to collide with neutral molecules (often helium, nitrogen or argon). In an embodiment according to the invention, the neutral etching agent molecules collide with high kinetic energy ion beam ions. The energy from the collision may be converted into internal energy which results in bond breakage and fragmentation of the etching agent into smaller fragments. The amounts of fragments typically increase with the acceleration energy of ions and their mass. When the energy of ion beam decreases to the low energy area (<5 keV), the amount of reactive elements decrease and volatile molecules as such C—O molecules may arise in the working chamber. These molecules may remain intact and do not significantly contribute to the inter-elemental reactions. When the total amount of reactive elements is decreased the etching rate is slowed down. Slowing down the etching rate together with lower penetration of surface of the semiconductor device may results in fine etching of the sample surface without the need to change the etching agent composition, concentration or injection pressure. Modern ion beam devices are capable of rapidly changing the beam energy, and thus it is possible to have very fast change between the normal dissimilar materials etching to very fine dissimilar material etching. This is beneficial for combined removal of the thick upper metal layers of a semiconductor device and the very dense lower semiconductor device metal layers or for better control of the end-point detection if the etching process is too fast.
For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
The embodiment of invention is a method for performing planar and cross-section etching by removing multiple layers of dissimilar materials like metals and dielectrics aiming to expose a single layer of interest or cross-sectioning several layers to perform various applications including but not limited to, nanoprobing, circuit edit and failure analysis.
Preferred embodiments of the present invention are directed to a method used for etching dissimilar materials used in the production of semiconductor devices. The utilization of the technique and the apparatus can be duplicated for uniform and smooth etching of dissimilar materials like copper, low-k dielectrics, GaAs, and GaN and others. The method is flexible and can be adapted as standalone or used in combination with other methods for enhanced productivity of etching or expedite techniques for probing analysis.
The number of oxidizing agents in the second etching agent is at most one element lower than the number reducing elements 20 in second the etching agent 23. If the metal 12 has lower etching rate compare to dielectric 14 the second etching agent comprises more oxidizing 19 elements needs to be supplied.
The number of oxidizing agents in the second etching agent is at most three elements higher than the number reducing elements 20 in second the etching agent 23.
In the preferred embodiments this second etching agent may be selected from the group comprise Ethyl Formate (o−r=−1), Diethyl Imidodicarbonate (o−r=−1), Acetic Acid (o−r=0), Hydrazine Acetate (o−r=2), water (o−r=1) or Ammonium Bicarbonate (o−r=3). The second etching agent is supplied until the same level of surface 16a and 16b is reached as shown in
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